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• W1991966135 abstract "Unsaturated 1,6-dicarbonyls like 2,4-hexadienedial are ring opening products in the OH initiated photo-oxidation of aromatic hydrocarbons. In the present study, the photolysis of E,Z- and E,E-2,4-hexadienedial has been investigated under natural sunlight conditions in a large volume outdoor reaction chamber. In the case of the E,Z-isomer, an extremely rapid isomerization into the E,E-form was observed. The photoisomerization frequency, relative to that of NO2, was found to be J(E,Z-2,4-hexadienedial)/J(NO2) = (0.148 ± 0.012). A more complex photolysis behavior was observed for E,E-2,4-hexadienedial. Here, a fast equilibrium preceded a comparably slow photolysis. For the equilibrium reaction, relative frequencies of J(E,E-2,4-hexadienedial → EQUI)/J(NO2) = (0.113 ± 0.009) and J(EQUI → E,E-2,4-hexadienedial)/J(NO2) = (0.192 ± 0.016) were obtained, giving an equilibrium constant of K = (0.59 ± 0.07). For the photolysis frequencies, ratios of J(E,E-2,4-hexadienedial → products)/J(NO2) = J(EQUI → products)/J(NO2) = (1.22 ± 0.45)·10−2 were determined. Qualitative aerosol measurements during the experiments showed that the photolysis of 2,4-hexadienedials is a source of secondary organic aerosol. In addition to the photolysis study, OH radical reaction rate constants were determined, values of (7.4 ± 1.9)·10−11 and (7.6 ± 0.8)·10−11 cm3 s−1 were obtained for E,Z- and E,E-2,4-hexadienedial, respectively. The results indicate that the dominant fate of E,Z-2,4-hexadienedial in the atmosphere will be photoisomerization, while for E,E-2,4-hexadienedial, both photolysis and OH radical reaction will be important sinks. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 689–697, 1999" @default.
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• W1991966135 date "1999-01-01" @default.
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• W1991966135 title "Kinetic study of the gas-phase photolysis and OH radical reaction of E,Z- and E,E-2,4-Hexadienedial" @default.
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• W1991966135 doi "https://doi.org/10.1002/(sici)1097-4601(1999)31:10<689::aid-jck2>3.0.co;2-p" @default.
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